Forum For Exchange Of Information On Enforcement
Compendium of analytical methods Recommended by the Forum to check compliance with Reach annex xvii restrictions March 2016 Version 1.0
Disclaimer The information contained in this document is intended solely as technical advice. This document does not create any substantive or procedural rights. The European Chemicals Agency (ECHA) does not accept any liability with regard to the information contained in this document. Usage of the information remains under the sole responsibility of the user. The information is subject to change. Parties using this document should be aware that there may be other acceptable alternatives for achieving and documenting compliance with the regulatory requirements under Annex XVII to REACH. Validity The present document is intended as a dynamic document. It will be revised at regular intervals to reflect changing technical standards, new available methods as well modifications of existing ones. The revisions will be published on ECHA website. ECHA Forum invites interested parties to submit additional information to be incorporated in future updates of this document. These can be submitted via
[email protected].
Version
Changes
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Version 1.0
First edition
March 2016
Compendium of analytical methods recommended by the forum to check compliance with Reach annex xvii restrictions Reference: ISBN: DoI: Date: Language:
ECHA-15-R-18-EN 978-92-9247-648-9 10.2823/399943 March 2016 English
© European Chemicals Agency, 2016
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Compendium of Analytical Methods
Preface The ECHA Forum aims at contributing to harmonised enforcement of Regulation (EC) No 1907/2006 – REACH, throughout the EU. Working in this framework the ECHA Forum decided to create a living database containing analytical methods that it recommends to check compliance with Annex XVII restrictions under REACH. The purpose of this document is to provide a ready reference of some available analytical methods that authorities or industry may use in order to assess the compliance of chemicals manufactured, used or placed on the European market to the restrictions set forth in Annex XVII to REACH. These methods for the analysis of chemicals are a collection of methods in use in the official laboratories supporting the Member States enforcement systems and in other laboratories linked to some stakeholders organisations consulted for this purpose. A data gathering survey amongst the cited parties was followed by an assessment conducted by expert members of the ECHA Forum Working Group on enforceability of restrictions. The methods have been scrutinised against performance requirements agreed by the Forum1 and taking into consideration the available information on sample preparation and analysis protocols and techniques. The methods judged suitable for checking compliance with restrictions are listed in this Compendium of analytical methods recommended by the ECHA Forum for checking compliance with REACH Annex XVII restrictions, hereinafter referred to as “Compendium”. The Compendium encompasses: •• Official methods (with references published in REACH legal text); •• Standard methods (published by International, European or National standardisation bodies); •• Methods published by a recognised technical organisation, a national or EU reference laboratory (EPA, etc.); •• Internal methods developed by the respondent laboratories. The methods included in the Compendium are recommended by the ECHA Forum to be used in the verification of compliance with the restrictions in order to ensure the quality and comparability of the analytical results. The Compendium of analytical methods recommended by the ECHA Forum for the enforcement of REACH restrictions is a tool offered by the Forum that all can use voluntarily thus evolving towards further harmonisation in the EU. Enforcement authorities, industry and public can benefit from such information.
1 Forum methodology for recommending analytical methods for enforcement of REACH Annex XVII restrictions, a summary is published at the Forum website echa.europa.eu/web/guest/about-us/who-we-are/enforcement-forum
3
Compendium of Analytical Methods
4
Table of Contents 1. INTRODUCTION TO THE COMPENDIUM
5
2. RATIONALE AND METHODOLOGY
5
3. HOW TO CONSULT THE COMPENDIUM
6
4. COMPENDIUM OF ANALYTICAL METHODS RECOMMENDED BY THE FORUM TO CHECK COMPLIANCE WITH REACH ANNEX XVII RESTRICTIONS
APPENDIX 1-GLOSSARY 1. List of acronyms 2. Key terms
8
45 45 46
Compendium of Analytical Methods
1. Introduction to the Compendium Article 67(1) of the REACH Regulation restricts the manufacture, placing on the market and use of certain hazardous substances, mixtures and articles. The dutyholders whose activities are subject to REACH restrictions should at all times be capable to check accurately and reliably if they comply with these obligations, for preventing negative impact of their activities on public health, on worker protection, on the environment, as well as on the free circulation of chemicals on the internal market. National enforcement authorities (NEAs) assess activities of the above natural and legal persons in the EU being their primary goal to detect violations of the communal acquis, for example, the restrictions enumerated in Annex XVII to REACH. In this context, the common need of all the parties is to determine accurately and reliably whether or not there is compliance with REACH restrictions. In addition, aiming at a level playing field in the EU, it is desirable that natural and legal persons are subject to a harmonised surveillance approach wherever in the EU territory. Few entries in Annex XVII to REACH specify which analytical method must be applied for checking the requirement set out in the restriction. That is why EU Member States have adopted over the past decennia analytical methods to be used by their NEAs, for those restrictions where no official analytical method is specified in the legal text. Some restrictions do not contain a limit value that needs to be checked, the so-called no-limit-value restrictions (NLV) and a case-by-case analysis is appropriate in those cases. To date, according to the experts of the Forum WG on the enforceability of restrictions, it remains unclear which analytical method should be applied for checking compliance with a NLV-restriction. As a consequence, those restrictions are currently covered in this compendium with certain limitations. In 2009, the European Commission invited the ECHA Forum members to communicate which analytical methods for checking compliance with REACH Annex XVII restrictions were accepted in their country. A compilation of the replies received constituted a first database of methods. This first inventory indicated that the number and variety of analytical methods used in different Member States were huge and in most of the cases a method accepted in one Member State was not automatically accepted by another Member State, thus the harmonised enforcement of REACH Annex XVII restrictions could be jeopardized. In June 2010, the Forum concluded on the need to produce a compendium for suitable analytical methods recommended to be used for the enforcement of restrictions.
2. Rationale and methodology With the view of producing guidance for suitable analytical methods for the enforcement of restrictions, as preliminary criteria for recommending methods, the Forum agreed the recommended methods should preferable be standardised ones. If such methods are not available, other methods can be used. The ECHA Forum has mandated a team of experts working under the supervision of the ECHA Forum (Forum WG Group on Enforceability of Restrictions) to first conceive a methodology for recommending analytical methods for enforcing REACH restrictions.
5
Compendium of Analytical Methods
6
The Forum methodology to recommend analytical methods for checking the compliance with REACH restrictions consisted first in the definition of a set of functional qualities (characteristics) of an analytical method. General principles applied in widely accepted international standards have been considered and a set of key performance characteristics have been identified for the purpose of assessing the suitability of an analytical method to check compliance with restrictions. The characteristics identified are: applicability, limit of detection, recovery, reproducibility and measurement uncertainty. For each of the selected characteristics, the Forum agreed upon generally acceptable performance requirements for analytical methods to be recommended. Widely accepted criteria have been applied to define the requirements for the considered characteristics of an analytical method to be suitable for checking compliance with REACH Annex XVII restrictions. Due to the broad ranges of products covered by REACH Annex XVII, and to the different limit values (including a total ban for certain substances) set forth in different REACH Annex XVII entries a case-bycase approach is applied where appropriate. The Forum also addressed the issue of NLV restrictions and adopted, as short term solution for assessing methods for NLV restrictions, to include in the Compendium the methods for which the applicability criteria are met and which show low limit of detection (LOD). Official methods (published in REACH legal text) are also included in the Compendium. Finally, while recognizing that for enforcement purpose a qualitative method cannot be conclusive and a confirmatory analysis is needed, the Forum decided to include in the Compendium qualitative analytical methods or techniques, with relevant LOD value accompanied by a note to make explicit reference to the qualitative method. The adopted Forum methodology was then implemented by the same experts to elaborate the Compendium of analytical methods recommended by the Forum for the enforcement of REACH Annex XVII restrictions. A data gathering survey was conducted among EU Member States and ECHA Accredited Stakeholders and, on the basis of the methodology, the reported analytical methods have been scrutinised by the Working Group with the aim of selecting objectively methods fit for the purpose. As foreseen by the adopted methodology, in few cases an expert judgment was applied and the selected methods have been considered suitable for the purpose of detecting the restricted substance, notwithstanding they slightly deviate from the performance requirements agreed upon by the ECHA Forum.
3. How to consult the Compendium TThe Compendium table in Chapter 4 of this document is divided in as many sections as there are entries in REACH Annex XVII. Each table section contains: •• The entry number followed by the substance or group of substances (analytes) under the scope of the restriction; •• The sub-entry number followed by the substance or group of substances (analytes) and the matrix or products under the scope of the restriction; •• The substance (analyte) under the scope of the reported method; •• The matrix or product under the scope of the reported method;
Compendium of Analytical Methods
7
•• The analytical method reported in the same format as referenced by regulations, standardization bodies or recognized technical organisations. Please note that for laboratory developed method the term “internal method” is used; •• The source for internal methods; •• The analytical technique or techniques; •• The sample preparation, if available; •• A note reporting the type of method. The methods “A” are fully adherent with the performance requirements agreed upon by the ECHA Forum; the methods “B” slightly deviate from the performance requirements agreed upon by the ECHA Forum; the methods “C” are official methods included in REACH legal text; the methods “D” are qualitative methods followed by the available LOD.
Note for qualitative methods Qualitative methods are analytical methods which allow to identify the presence of a substance on the basis of its chemical, biological or physical properties. These methods do not enable a conclusive judgement for enforcement purpose and entail a confirmatory analysis. For some entries, the Compendium contains qualitative analytical methods (or techniques, when this is the only available information) accompanied with available LOD values. Those methods are marked as “D” in the column “note”. In general, according to the Forum methodology it is not possible to conclude on the recommendability of the qualitative methods. A qualitative method could be used to screen potential non-compliant goods but a positive result cannot be conclusive for enforcement purpose and a confirmatory analysis is deemed necessary. For a better consultation of the Compendium table please refer also to Appendix 1 to this document, which contains the list of abbreviation and relevant definitions of terms used in the document.
Compendium of Analytical Methods
8
4. Compendium of analytical methods recommended by the Forum to check compliance with REACH Annex XVII Restrictions Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Internal method
DIN EN 12766
GC-ECD
SPE
B
Internal method
DIN EN ISO 6401
GC-FID or GCMS
no
A
1. Polychlorinated terphenyls (PCTs) 1.substances/mixtures including waste oils, equipment PCT
non-aqueous liquids
2. Chloroethene (vinyl chloride) CAS No 75-01-4 ; EC No 200-831-0 2.Propellant in aerosols vinyl chloride
gas
3. Liquid substances or mixtures which are regarded as dangerous in accordance with Directive 1999/45/EC or are fulfilling the criteria for any of the following hazard classes or categories set out in Annex I to Regulation (EC) No 1272/2008: (a) hazard classes 2.1 to 2.4, 2.6 and 2.7, 2.8 types A and B, 2.9, 2.10, 2.12, 2.13 categories 1 and 2, 2.14 categories 1 and 2, 2.15 types A to F; (b) hazard classes 3.1 to 3.6, 3.7 adverse effects on sexual function and fertility or on development, 3.8 effects other than narcotic effects, 3.9 and 3.10; (c) hazard class 4.1; (d) hazard class 5.1. 3.3. liquid substances or mixtures liquid substance and mixtures
non-aqueous liquids
DIN 51562 Viscometry Measurement of kinematic viscosity by means of the Ubbelohde viscometer
viscometry
without
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
9
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Tris (2,3 dibromopropyl) phosphate
textiles
Internal method
DIN EN 16377
GC-MS
solvent extraction
A
Tris (2,3 dibromopropyl) phosphate
textiles, plastics
Internal method
DIN EN 71 - safety of toys, part 10
GC-MS
extraction with A acetonitrile, filtration
Benzene
polymers/toys
ASTM D4526-12
HS GC-FID
Extraction
A
Benzene
toys
DIN EN 71-11
GC-MS
Headspace or Purge & Trap
A
Benzene
toys
MSZ EN 7111:2006
GC-MS
Extraction
A
Benzene
mixtures of xylenes
ASTM D 65632012
GC-FID
n.d
A
Benzene
cynoacrylate glues
Internal method
GC-MS
Dilution in acetone
A
4. Tris (2,3 dibromopropyl) phosphate CAS No 126-72-7 4.1. Textile articles
5. Benzene CAS No 71-43-2 5.1 and 5.2 Toys /parts of toys
5.3 substances/mixtures
CY-SGL method “METH 11 01 11”, accredited according to EN ISO 17025:2005
Compendium of Analytical Methods
10
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Benzene
mixtures
Crocidolite
Reference for internal methods
Analytical technique
Sample preparation
Note
EPA 8260C
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
Asbestos fibres (only in solid samples)
NIOSH 9002
PLM (polarized microscopy)
A
Amosite
Asbestos fibres (only in solid samples)
NIOSH 9002
PLM (polarized microscopy)
A
Anthophyllite
Asbestos fibres (only in solid samples)
NIOSH 9002
PLM (polarized microscopy)
A
Actinolite
Asbestos fibres (only in solid samples)
NIOSH 9002
PLM (polarized microscopy)
A
6. Asbestos fibres (a) Crocidolite CAS No 12001-28-4 (b) Amosite CAS No 12172-73-5 (c) Anthophyllite CAS No 77536-67-5 (d) Actinolite CAS No 77536-66-4 (e) Tremolite CAS No 77536-68-6 (f) Chrysotile CAS No 12001-29-5 CAS No 132207-32-0 6.1. Fibres / articles
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
11
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Tremolite
Asbestos fibres (only in solid samples)
NIOSH 9002
PLM (polarized microscopy)
A
Chrysotile
Asbestos fibres (only in solid samples)
NIOSH 9002
PLM (polarized microscopy)
A
Asbestos
construction material/soil/ powder
SEM-EDS
Depending on the sample
N/A
7. Tris(aziridinyl)phosphinoxide CAS No 545-55-1 ; EC No 208-892-5 7.1. and 7.2. Textile articles Tris(aziridinyl) phosphinoxide
textiles
Internal method
DIN EN 16377
GC-MS
solvent extraction
A
Internal method
DIN EN 16377
GC-MS
solvent extraction
A
GC-MS
Reduction with A sodium ditionite and extraction with MTBE
8. Polybromobiphenyls; Polybrominatedbiphenyls (PBB) CAS No 59536-65-1 8.1. and 8.2. Textile articles PBBs
textiles
12. 2-Naphthylamine CAS No 91-59-8 ; EC No 202-080-4 and its salts 12. substances/mixtures 2-Napthylamine
liquids: Tattoo inks and pmu products; solids: leather
EN ISO 172341:2010
Compendium of Analytical Methods
12
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
13. Benzidine CAS No 92-87-5 ; EC No 202-199-1 and its salts 13. substances/mixtures Benzidine
liquids: Tattoo inks and pmu products; solids: leather
EN ISO 172341:2010
GC-MS
Reduction with A sodium ditionite and extraction with MTBE
Mercury
paints, preservation of wood
ISO 3856/71984
HG-AAS
acid extraction
Mercury
paints
18. Mercury compounds 18. substances and mixtures
XRF/XRD
A
D /5%
18a. Mercury CAS No 7439-97-6 EC No 231-106-7 18a.1. Substance Mercury
pure element
Internal method
Mercury
solids, solutions, apparel products
EPA 7473
paints
ISO 17294-2
AMA 254 by Altec Ltd. 2002
AAS AAS
homogenisation
A A
19. Arsenic compounds 19.1. and 19.2. Substances and mixtures Arsenic 19.3. wood
D / 0.05 %
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
13
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
paints
Internal method
ISO 17353
GC-MS/MS
Sample preparation
Note
20. Organostannic compounds 20.1, 20.2 and 20.3 substances/mixtures Organostannic compounds 20.4 substances in articles Tri-substituted organostannic compounds 20.5 substances in mixtures and articles Dibutyltin (DBT) compounds 20.6 substances in articles Dioctyltin (DOT) compound 21. Di-μ-oxo-di-n-butylstanniohydroxyborane/Dibutyltin hydrogen borate C8H19BO3Sn (DBB) substances/mixtures
B
Compendium of Analytical Methods
14
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
GC-MS
liquid: derivatisation A and SPE . Solids: soxhlet extraction and derivatisation
22. Pentachlorophenol CAS No 87-86-5 ; EC No 201-778-6 and its salts and esters 22. substances/constituent of substances /mixtures Pentachlorophenol
liquids and solids EN 12673
Pentachlorophen
solids
Internal method
US EPA 8041, US EPA 3500, DIN ISO 14154
GC-MS
Direct injection (extraction and derivatization)
A
Pentachlorophen
aqueous liquids
Internal method
US EPA 8041, US EPA 3500, ČSN EN 12673
GC-MS
Direct injection (extraction and derivatization)
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
15
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
ICP-MS (ISmethod)
1. shred the material A to pieces <5mm 2. transfer 100mg material to microwave vessel and add 5ml HNO3 and 2ml H2O2) 3. microwave digestion 4. dilute to 50ml with H2O 5. add internal standard and dilute to appropriate concentration range
23. Cadmium CAS No 7440-43-9 EC No 231-152-8 and its compounds 23.1 Cadmium in plastic material Cadmium
plastics
DIN EN 62321; VDE 00421:2009-12:200912 Electrotechnical products Determination of levels of six regulated substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers) (IEC 62321:2008); German version EN 62321:2009
Cadmium
plastics
Internal method
EN-1122
FLAME ATOMIC Acid (c. H2SO4 and c. ABSORPTION HNO3) digestion in a microwave oven
A
Compendium of Analytical Methods
16
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Cadmium
plastics
Internal method
EN-1122
FLAME ATOMIC Acid (c. H2SO4 and c. ABSORPTION HNO3) digestion in a microwave oven
A
Cadmium
plastics
Internal method
plastic: PN-EN 1122:2004 Plastics. Determination of cadmium. Wet decomposition method;
AAS
plastic: digestion in muffle oven
A
Cadmium
plastics (not polyfluorinated plastic)
Internal method
SFS-EN 1122:2001: Plastics.Determination of cadmium. Wet decomposition method.
ICP-OES
Wet digestion with A concentrated H2SO4 and 30 % H2O2. After digestion sample is diluted with water.
metals, alloys, metal coatings
Internal method
ICP-OES) (ISO 11885:2007) БДС EN ISO 11885:2009
ICP-OES
Microwave decomposition of the matrix to acid solution of cations
23.8 Brazing fillers and 23.10 Jewellery Cadmium
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Cadmium
Total Cadmium
17
Matrix/Product
metals
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Internal method
Electrotechnical products. Determination of levels of six regulated substances (lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ethers)
AAS
metal: acid digestion in open vessel
A
EDXRF
plastics, paints, aqueous liquids, wood, leather, paper and metals
D / 50 ppm
24. Monomethyl — tetrachlorodiphenyl methane ; Trade name: Ugilec 141 ; CAS No 76253-60-6 24.1. substances/mixtures Monomethyl — tetrachlorodiphenyl methane Trade name: Ugilec 141
non-aqueous liquids
Internal method
DIN EN 12766
GC-ECD
SPE
A
Internal method
DIN EN 12766
GC-ECD
SPE
A
25. Monomethyl-dichloro-diphenyl methane ; Trade name: Ugilec 121 ; Ugilec 21 25. substances/mixtures Monomethyl-dichlorodiphenyl methane Trade name: Ugilec 121 Ugilec 21
non-aqueous liquids
Compendium of Analytical Methods
18
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
SPE
A
26. Monomethyl-dibromo-diphenyl methane bromobenzylbromotoluene, mixture of isomers ; Trade name: DBBT ; CAS No 99688-47-8 26. substances/mixtures Monomethyldibromo-diphenyl methane bromobenzyl bromotoluene, mixture of isomers
non-aqueous liquids
Internal method
DIN EN 12766
GC-ECD
Trade name: DBBT; 27. Nickel CAS No 7440-02-0 EC No 231-111-4 and its compounds 27. 1 and 27.2 substance in post assemblies which are inserted into pierced parts of the human body and articles intended to come into direct and prolonged contact with the skin Nickel
post assemblies which are inserted into pierced parts of the human body and articles intended to come into direct and prolonged contact with the skin
EN 1811:2011 + A1:2015 - OJ C 14 of 15/01/2016 p. 110
C
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
19
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Nickel
parts of spectacle frames and sunglasses intended to come into close and prolonged contact with the skin
EN 16128:2011 - OJ C 14 of 15/01/2016 p. 110
C
Nickel
simulation of wear and corrosion for the detection of nickel release from coated items
EN 12472:2005 + A1:2009- OJ C 14 of 15/01/2016 p. 110
C
28. Substances which appear in Part 3 of Annex VI to Regulation (EC) No 1272/2008 classified as carcinogen category 1A or 1B (Table 3.1) or carcinogen category 1 or 2 (Table 3.2) and listed as follows: - Carcinogen category 1A (Table 3.1)/carcinogen category 1 (Table 3.2) listed in Appendix 1; - Carcinogen category 1B (Table 3.1)/carcinogen category 2 (Table 3.2) listed in Appendix 2 28.1. substances/constituents of substances/mixtures Benz(a)anthracene
solids
Internal method
US EPA 8270
GC-MS
Direct injection (Extraction technique)
A
Benz(a)anthracene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
Compendium of Analytical Methods
20
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Benzene
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Benzo(a)pyrene
solids
Internal method
US EPA 8270,
GC-MS
Direct injection (Extraction technique)
A
Benzo(a)pyrene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
Benzo(b)fluoranthene
solids
Internal method
US EPA 8270
GC-MS
Direct injection (Extraction technique)
A
Benzo(b)fluoranthene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
Benzo(k)fluoranthene
solids
Internal method
US EPA 8270
GC-MS
Direct injection (Extraction technique)
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
21
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Benzo(k)fluoranthene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
Chrysene
solids
Internal method
US EPA 8270
GC-MS
Direct injection (Extraction technique)
A
Chrysene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
Dibenz(a.h)anthracene
solids
Internal method
US EPA 8270
GC-MS
Direct injection (Extraction technique)
A
Dibenz(a.h)anthracene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
1.2-Dibromo-3Chloropropane
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Compendium of Analytical Methods
22
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
1.2-Dibromoethane (EDB)
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
1.2-Dichloroethane
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Hexachlorobenzene (HCB)
solids
Internal method
US EPA 8081
GC-ECD
Liquid extraction
A
Hexachlorobenzene (HCB)
liquids
Internal method
US EPA 8081
GC-ECD
Liquid extraction
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
23
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Trichloroethene
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Vinyl chloride
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Compendium of Analytical Methods
24
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
29. Substances which appear in Part 3 of Annex VI to Regulation (EC) No 1272/2008 classified as germ cell mutagen category 1A or 1B (Table 3.1) or mutagen category 1 or 2 (Table 3.2) and listed as follows: — Mutagen category 1A (Table 3.1)/ mutagen category 1 (Table 3.2) listed in Appendix 3 ; — Mutagen category 1B (Table 3.1)/ mutagen category 2 (Table 3.2) listed in Appendix 4 29.1. substances/constituents of substances/mixtures Benzene
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Benzo(a)pyrene
solids
Internal method
US EPA 8270
GC-MS
Direct injection (Extraction technique)
A
Benzo(a)pyrene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
1.2-Dibromo-3Chloropropane
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
25
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
30. Substances which appear in Part 3 of Annex VI to Regulation (EC) No 1272/2008 classified as toxic to reproduction category 1A or 1B (Table 3.1) or toxic to reproduction category 1 or 2 (Table 3.2) and listed as follows: - Reproductive toxicant category 1A adverse effects on sexual function and fertility or on development (Table 3.1) or reproductive toxicant category 1 with R60 (May impair fertility) or R61 (May cause harm to the unborn child) (Table 3.2) listed in Appendix 5 - Reproductive toxicant category 1B adverse effects on sexual function and fertility or on development (Table 3.1) or reproductive toxicant category 2 with R60 (May impair fertility) or R61 (May cause harm to the unborn child) (Table 3.2) listed in Appendix 6 30.1. substances/constituent of substances/mixtures Benzo(a)pyrene
solids
Internal method
US EPA 8270
GC-MS
Direct injection (Extraction technique)
A
Benzo(a)pyrene
liquids
Internal method
US EPA 8270, EN ISO 6468
GC-MS
Direct injection (Extraction technique)
A
Bis(2-ethylhexyl) phthalate
solids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Bis(2-ethylhexyl) phthalate
liquids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Butyl benzyl phthalate
solids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Butyl benzyl phthalate
liquids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Compendium of Analytical Methods
26
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
1.2-Dibromo-3Chloropropane
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
Di-isobutylphthalate
solids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Di-isobutylphthalate
liquids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Di-n-butyl phthalate
solids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Di-n-butyl phthalate
liquids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Di-pentylphthalate
solids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
27
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
Di-pentylphthalate
liquids
Internal method
US EPA 8061
GC-MS
Direct injection (Extraction technique)
A
1.2.3-Trichloropropane
solids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (sample is extracted with defined volume of methanol, aliquot volume of sample is transferred into the headspace vial with defined volume of water and internal standards are added)
A
31. (a) Creosote; wash oil CAS No 8001-58-9 EC No 232-287-5 (b) Creosote oil; wash oil CAS No 61789-28-4 EC No 263-047-8 (c) Distillates (coal tar), naphthalene oils; naphthalene oil CAS No 84650-04-4 EC No 283-484-8 (d) Creosote oil, acenaphthene fraction; wash oil CAS No 90640-84-9 EC No 283-484-8EC No 292-605-3 (e) Distillates (coal tar), upper; heavy anthracene oil CAS No 65996-91-0 EC No 266-026-1 (f) Anthracene oil CAS No 90640-80-5 EC No 292-602-7 (g) Tar acids, coal, crude; crude phenols CAS No 65996-85-2 EC No 266-019-3 (h) Creosote, wood CAS No 8021-39-4 EC No 232-419-1 (i) Low temperature tar oil, alkaline; extract residues (coal), low temperature coal tar alkaline CAS No 122384-78-5 EC No 310-191-5 31.1. substances/mixtures/wood benz(a)pirene, PAHs, phenol
wood
MSZ EN 10143:1999*; MSZ 1014-4:1999*
HPLC-UV or HPLC-FLD
solid-liquid extraction and SPE
A
benz(a)pirene, PAHs, phenol
aqueous liquids
EPA 550.1; MSZ 1484-9:2009
HPLC-UV or HPLC-FLD
SPE
A
Compendium of Analytical Methods
28
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
32. Chloroform CAS No 67-66-3 EC No 200-663-8 32.1. substances/constituents of substances / mixtures Chloroform
cyanoacrylate glues
Internal method
CY-SGL method “METH 11 01 11”, accredited according to EN ISO 17025:2005
GC-MS
Dilution in acetone
A
Chloroform
aqueous liquids
Internal method
US EPA 8260, US EPA 5021A, US EPA 5021, US EPA 8015, MADEP 2004, rev. 1.1, ISO 15009
HSGC-MS or HSGC-FID
Headspace (noextraction step, sample is just transferred into the headspace vial and internal standards are added)
A
Chloroform
mixtures (nonaqueous and aqueous liquids)
EPA METHOD 8260C
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
EPA METHOD 8260C
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
GC-MS
~ 0,05 g sample / 100 ml solvent
D/ 0.04%
34. 1,1,2-Trichloroethane CAS No 79-00-5 EC No 201-166-9 34.1. substances/constituents of substances / mixtures 1,1,2-Trichloroethane
mixtures (nonaqueous and aqueous liquids)
1,1,2-Trichloroethane
adhesives, paints,
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
29
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
GC-MS
~ 0,05 g sample / 100 ml solv.
D/ 0.04%
35. 1,1,2,2-Tetrachloroethane CAS No 79-34-5 EC No 201-197-8 35.1. substances/constituents of substances / mixtures 1,1,2,2Tetrachloroethane
mixtures (nonaqueous and aqueous liquids)
EPA METHOD 8260C
1,1,2,2-
adhesives, paints,
Tetrachloroethane
aqueous liquids
Internal method
US EPA 624, US EPA 8260
HSGC-MS or HSGC-FID
Headspace (noextraction step, sample is just transferred into the headspace vial and internal standards are added)
A
1,1,2,2Tetrachloroethane
aqueous liquids
Internal method
US EPA 624, US EPA 8260
HSGC-MS or HSGC-FID
Headspace (noextraction step, sample is just transferred into the headspace vial and internal standards are added)
A
Compendium of Analytical Methods
30
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
36. 1,1,1,2-Tetrachloroethane
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
US EPA 624, US EPA 8260
HSGC-MS or HSGC-FID
Headspace (noextraction step, sample is just transfered into the headspace vial and internal standards are added)
A
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
GC-MS
~ 0,05 g sample / 100 ml solv.
D/ 0.04%
GC-MS
~ 0,05 g sample / 100 ml solv.
D/ 0.04%
CAS No 630-20-6
36.1. substances/constituents of substances / mixtures 1,1,1,2Tetrachloroethane
aqueous liquids
Internal method
1,1,1,2Tetrachloroethane
mixtures (nonaqueous and aqueous liquids)
EPA METHOD 8260C
1,1,1,2Tetrachloroethane
adhesives, paints,
37. Pentachloroethane CAS No 76-01-7 EC No 200-925-1 37.1. substances/constituents of substances / mixtures Pentachloroethane
adhesives, paints,
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
31
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
US EPA 624, US EPA 8260
HPLC-UV or HPLC-FLD
Headspace (noextraction step, sample is just transferred into the headspace vial and internal standards are added)
A
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
GC-MS
~ 0,05 g sample / 100 ml solv.
D/ 0.04%
38. 1,1-Dichloroethene CAS No 75-35-4 EC No 200-864-0 38.1. substances/constituents of substances / mixtures 1,1-Dichloroethene
aqueous liquids
Internal method
1,1-Dichloroethene
mixtures (nonaqueous and aqueous liquids)
EPA METHOD 8260C
1,1-Dichloroethene
adhesives, paints,
43. Azocolourants and Azodyes 43.aromatic amines listed in Appendix 8 of REACH in textile and leather articles or dyed parts thereof 4-aminoazobenzene
leather
EN ISO 17234-1 2010
C
leather
EN ISO 172342:2011
C
textiles
EN 143621:2012
C
textiles
EN 143623:2012
C
Compendium of Analytical Methods
32
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
GC/MS
solvent extraction
B
45. Diphenylether, octabromo derivative C12H2Br8O 45.1. substances / constituents of substances / mixtures 45.2. articles / flame-retardant parts of articles PBBs
textiles
DIN EN 16377
47. Chromium VI compounds 47.1. Cement and cement containing mixtures Chromium VI
cement and cement containing mixtures
EN 196-10:2006 - OJ C23, 28.1.2005, p.8
C
48. Toluene CAS No 108-88-3; EC No 203-625-9 48. (substances / mixtures) in adhesives or spray paints Toluene
cyanoacrylate glues
Internal method
CY-SGL method “METH 11 01 11”, accredited according to EN ISO 17025:2005
GC-MS
Dilution in acetone
A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
33
Analyte
Matrix/Product
Analytical method
Toluene
paints
PN-EN ISO 11890-2:201306E
Toluene
adhesives and spray paints
Internal method
mixtures (nonaqueous liquids)
EPA METHOD 8260C
Reference for internal methods
PN-EN ISO 11890-2
Analytical technique
Sample preparation
Note
GC-FID
preparation of the sample according to PN-EN-ISO 1513:2010P, analysis according PN-EN ISO 11890-2:201306E extraction of toluene from paints using methanol and dichloromethane (2:3); centrifugation of the sample
A
GC-FID or GCMS
Sample (1-2g) was weighed in a tube with accuracy of 0,01mg and diluted with an appropriate amount of solvent. The content of the tube was then homogenized by vortexing.
A
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
49. Trichlorobenzene CAS No 120-82-1 ; EC No 204-428-0 49. substances / mixtures 1,2,3-Trichlorobenzene and 1,2,4-Trichlorobenzene
Compendium of Analytical Methods
34
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Trichlorobenzene
adhesives, paints,
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
GC-MS
~ 0,05 g sample / 100 ml solv.
D/ 0.04%
50.Polycyclic-aromatic hydrocarbons (PAH) (a) Benzo[a]pyrene (BaP) CAS No 50-32-8 (b) Benzo[e]pyrene (BeP) CAS No 192-97-2 (c) Benzo[a]anthracene (BaA) CAS No 56-55-3 (d) Chrysen (CHR) CAS No 218-01-9 (e) Benzo[b]fluoranthene (BbFA) CAS No 205-99-2 (f) Benzo[j]fluoranthene (BjFA) CAS No 205-82-3 (g) Benzo[k]fluoranthene (BkFA) CAS No 207-08-9 (h) Dibenzo[a,h]anthracene (DBAhA) CAS No 53-70-3 2 50.1. Extender oils Polycyclic aromatic extract (PCA)
extender oils
Petroleum Standard IP346:1998. This standard can be used only until 23 September 2016
C
PAH
extender oils
EN 16143:2013
C
vulcanised rubber
ISO 21461 (Rubber vulcanised – Determination of aromatic oil in vulcanised rubber compounds)
C
50.2. Tyres and treads for retreading Bay protons
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
35
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
51. The following phthalates (or other CAS and EC numbers covering the substance): (a) Bis (2-ethylhexyl) phthalate (DEHP) CAS No 117-81-7 ; EC No 204-211-0 (b) Dibutyl phthalate (DBP) CAS No 84-74-2 EC No 201-557-4 (c) Benzyl butyl phthalate (BBP) CAS No 85-68-7 EC No 201-622-7 51.1 Plasticised materials for toys and childcare articles production; 51.2 Plasticised materials in toys and childcare article DEHP DBP BBP
plastics
Internal method
SW05OF01: SANDRA BIEDERMANN-BREM, MAURUS BIEDERMANN, KATELL FISELIER, & KONI GROB; Compositional GC-FID analysis of the additives to PVC, focusing on the gaskets of lids for glass jars; Food Additives and Contaminants, December 2005; 22(12): 1274– 1284 IT07EC01: Z. Ezerskisa, V. Morkunas, M. Suman, C. Simoneau; Analytical screening of polyadipates and other plasticisers in poly(vinyl chloride) gasket seals and in fatty food by gas chromatography–mass spectrometry; Analytica chimica acta; 604 (2007); 29–38
GC-MS
sample preparation: EN 14372:2005 (non PVC plastics) and SW05OF01 (PVC) + instrumental analysis IT07EC01 EN 14372:2005: Soxhlet extraction of the plastic with diethylether SW05OF01: Dissolution of the PVC in tetrahydrofuran, precipitation PVC by ethanol
A
Compendium of Analytical Methods
36 Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
DEHP DBP BBP
plastics
CPSCCH-C1001-09.1
n.a
GC-MS
solvent extraction
A
DEHP BBP DBP
PVC toys and Internal method childcare articles
1. shred the material to pieces <5mm 2. dissolve in THF 3. precipitate PVC with ethanol 4. centrifugate and then dilute solution with cyclohexane
A
Sample preparation: GC-MS (EI) 1. USA Test Method: CPSCCH-C1001-09.1 (2009), USA Test Method: CPSCCH-C1001-09.3 (2010) 2. Plasicizers in PVC Toys and Childcare Products: What Succeeds the Phthalates? Market Survey 2007, Sandra BiedermannBrehm, Maurus Biedermann, Susanne Pfenninger, Martin Bauer, Werner Altkofer, Karls Rieger, Urs Hauri, Christian Droz, Koni Grob, Chromatographia 2008, 68, August (No. ¾), Vieweg + Teuber, GWV Fachverlage GmbH. Analytical method: VDI 4301 Blatt 6:2012-09 Measurement of indoor air pollution - Measurement of phthalates with GC/MS (VDI guideline)
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
37
Analyte
Matrix/Product
DEHP BBP DBP
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
PVC in toys and Internal method childcare articles
EN 12586:2007+A1: 2011Child use and care articles. Soother holder. Safety requirements and test methods
GC-MS
A Softeners are extracted from the plastic with diethyl ether. Extracted softeners are diluted with cyclohexane and analyzed with GC-MS.
DEHP BBP DBP
PVC
Internal method
CPSC-CH-C1001-09.2
GC-MS
Dissolve in tetrahydrofuran and precipitate in hexane
A
DEHP DBP BBP
polyvinyl chloride
Internal method
EPA method 8061A, PNEN 15777:2009
GC-FID
solid-liquid extraction (soxtec)
A
Compendium of Analytical Methods
38 Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
sample preparation: EN 14372:2005 (non PVC plastics) and SW05OF01 (PVC) + instrumental analysis IT07EC01
A
52. The following phthalates (or other CAS- and EC numbers covering the substance): (a) Di-‘isononyl’ phthalate (DINP) CAS No 28553-12-0 and 68515-48-0 ; EC No 249-079-5 and 271-090-9 (b) Di-‘isodecyl’ phthalate (DIDP) CAS No 26761-40-0 and 68515-49-1 EC No 247-977-1 and 271-091-4 (c) Di-n-octyl phthalate (DNOP) CAS No 117-84-0 EC No 204-214-7 52.1 Plasticised materials for toys and childcare articles production; 52.2 Plasticised materials in toys and childcare article DINP DIDP DNOP
plastics
sample preparation: EN 14372:2005 (non PVC plastics) and SW05OF01 (PVC) + instrumental analysis IT07EC01
SW05OF01: SANDRA BIEDERMANN-BREM, MAURUS BIEDERMANN, KATELL FISELIER, & KONI GROB; Compositional GC-FID analysis of the additives to PVC, focusing on the gaskets of lids for glass jars; Food Additives and Contaminants, December 2005; 22(12): 1274– 1284 IT07EC01: Z. Ezerskisa, V. Morkunas, M. Suman, C. Simoneau; Analytical screening of polyadipates and other plasticisers in poly(vinyl chloride) gasket seals and in fatty food by gas chromatography–mass spectrometry; analytica chimica acta; 6 0 4 ( 2 0 0 7 ); 29–38
GC coupled with MS
EN 14372:2005: Soxhlet extraction of the plastic with diethylether SW05OF01: Dissolution of the PVC in tetrahydrofuran, precipitation PVC by ethanol
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
39
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
DINP DIDP DNOP
plastic toys, FCMA
Internal method
ČSN EN 15777
GC-ECD, GCMS
Soxhlet extraction in diethylether
A
DINP DIDP DNOP
plastics
CPSCCH-C1001-09.1
GC/MS
solvent extraction
A
Compendium of Analytical Methods
40
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
DINP DIDP DNOP
PVC toys and childcare products
Internal method
Sample preparation: 1. USA Test Method: CPSCCH-C1001-09.1 (2009), USA Test Method: CPSCCH-C1001-09.3 (2010) 2. Plasicizers in PVC Toys and Childcare Products: What Succeeds the Phthalates? Market Survey 2007, Sandra Biedermann-Brehm, Maurus Biedermann, Susanne Pfenninger, Martin Bauer, Werner Altkofer, Karls Rieger, Urs Hauri, Christian Droz, Koni Grob, Chromatographia 2008, 68, August (No. ¾), Vieweg + Teuber, GWV Fachverlage GmbH. Analytical method:VDI 4301 Blatt 6:201209 Measurement of indoor air pollution - Measurement of phthalates with GC/MS (VDI guideline)
Analytical technique
Sample preparation
Note
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
41
Analyte
Matrix/Product
DINP DIDP DNOP
DNOP
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
PVC in toys and Internal method childcare articles
EN 12586:2007 + A1: 2011Child use and care articles. Soother holder. Safety requirements and test methods
GC-MS
A Softeners are extracted from the plastic with diethyl ether. Extracted softeners are diluted with cyclohexane and analyzed with GC-MS.
toys and Internal method childcare articles;- plastics
1) G.O. Adewuyi et al. The pacific J. Of Science and Technology, Vol.13 (2), 2012: 251; 2) Ying-Sing Fung et al., Fresenius J.Anal.Chem. (1994) 350: 721-723; 3) S.Marten, M.Naguschewski, Knauer Application Note 05/2010; 4) Y.J.Yao et al., Env. Mon. And Ass. 19: 83-91, 1991
HPLC-UV
Sample preparation CPSCCH-C1001-09.3 + instrumental analysis IT12ML01
CPSC-CH-C1001-09.2
GC-MS
Dissolve in tetrahydrofuran and precipitate in hexane
A
GC-MS
MW extraction followed by GCMS with internal standard
A
DINP DIDP DNOP
PVC
Internal method
DINP DIDP DNOP
paints, plastics, paper, textiles
CPSCCH-C1001-09.3
Note
A
Extraction with organic solvent (Tetrahydrofuran)
Compendium of Analytical Methods
42
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
DIN 55682:200-12 ; DIN 55683:2009-08
GC-MS
Solvent extraction
A
DIN 55682:200-12 ; DIN 55683:2009-08
GC-MS
solvent extraction
A
54. 2-(2-methoxyethoxy)ethanol (DEGME) CAS No 111-77-3 ; EC No 203-906-6 54. Constituent of paints, paint strippers, cleaning agents, self-shining emulsions or floor sealants 2-(2-methoxyethoxy) ethanol (DEGME)
paints, paint strippers, cleaning agents, self-shining emulsions and floor sealants
Internal method
55. 2-(2-butoxyethoxy)ethanol (DEGBE) CAS No 112-34-5 EC No 203-961-6 55.1. Constituent of spray paints or spray cleaners in aerosol dispensers 2-(2-butoxyethoxy) ethanol (DEGBE)
spray paints or spray cleaners in aerosol dispensers
Internal method
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
43
Matrix/Product
Analytical method
56. Methylenediphenyl diisocyanate (MDI) CAS No 26447-40-5 EC No 247-714-0 56.1. Constituent of mixtures Internal method Methylenediphenyl adhesives diisocyanate and sealants including hotmelts, One Component Foams (OCF) in pressurized cans, semi-solid products and pre-polymers
Reference for internal methods
Analytical technique
Sample preparation
Note
Humberto E. Ferreira, José Condeço, Inês Fernandes, David Duarte and João Bordado, HPLC-UV and HPLC-ESI+-MS/ MS analysis of free monomeric methylene diphenyl diisocyanate in Polyurethane Foams and Prepolymers after stabilization with NBMA a new derivatizating agent , Anal. Methods, 2014, Accepted Manuscript, 2014, DOI: 10.1039/C4AY01163E
Sample prep conducted in ambient air, with anhydrous acetonitrile dissolution. Pre-column derivatization with an excess of secondary aromatic amine (N MethylBenzylA mine or NBMA), without catalist, for 90 minutes, followed by an HPLC separation, with UV254nm detection and quantitation. The method does not use toluene, xylene, DMF, DMSO or chlorinated solvents.
A Sample prep conducted in ambient air, with anhydrous acetonitrile dissolution of 1500mg aliquote, or 600mg aliquote (pre-polymers). Precolumn derivatization with a 5 times molar excess of secondary aromatic amine (NMethylBenzylA mine or NBMA), without catalist, for 90 minutes. Dilutions in acetonitrile.
44
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Compendium of Analytical Methods
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Methylenediphenyl diisocyanate
adhesives and sealants including hotmelts, One Component Foams (OCF) in pressurized cans, semi-solid products and pre-polymers
Internal method
Humberto E. Ferreira, José Condeço, Inês Fernandes, David Duarte and João Bordado, HPLC-UV and HPLC-ESI+-MS/ MS analysis of free monomeric methylene diphenyl diisocyanate in Polyurethane Foams and Prepolymers after stabilization with NBMA a new derivatizating agent , Anal. Methods, 2014, Accepted Manuscript, 2014, DOI: 10.1039/C4AY01163E
Sample prep conducted in ambient air, with anhydrous acetonitrile dissolution. Pre-column derivatization with an excess of secondary aromatic amine (NMethylBenzylA mine or NBMA), without catalist, for 90 minutes, followed by an HPLC separation, with Mass Spectrometry detection, identification and quantitation (MS/MS). The method does not use toluene, xylene, DMF, DMSO or chlorinated solvents.
Sample preparation
Note
A Sample prep conducted in ambient air, with anhydrous acetonitrile dissolution of 1500mg aliquote, or 600mg aliquote (pre-polymers). Precolumn derivatization with a 5 times molar excess of secondary aromatic amine (NMethylBenzylA mine or NBMA), without catalist, for 90 minutes. Dilutions in acetonitrile.
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
45
Matrix/Product
Analytical method
Reference for internal methods
Analytical technique
Sample preparation
Note
HSGC-ECD or HSGC-MS
Purge & Trap or HS
B
GC-MS
~ 0,05 g sample / 100 ml solv.
D/ 0.04%
57. Cyclohexane CAS No 110-82-7 EC No 203-806-2 57.1. Constituent of neoprene-based contact adhesives Cyclohexane
neoprenebased contact adhesives
Cyclohexane
adhesives, paints,
DIN EN ISO 10301 (F4)
58. Ammonium nitrate (AN) CAS No 6484-52-2 EC No 229-347-8 58.1. (Substances / mixtures) for use as a solid fertilizer, straight or compound Nitrogen
hydrochloric acid solution of ammonium nitrate
BSS EN15750:2010 Method А; BSS 5172:1989 т.4.2
Distillation apparatus. Automatic titrator.
Reduction, hydrolysis, A distillation, titration
Nitrogen
aqueous solution of ammonium nitrate
BSS EN15475:2009; BSS 5172:1989 т.4.2
Distillation apparatus. Automatic titrator.
Distillation, titration
Calculative method according to 2003/2003, Annex IV method 2.6.2
Calculative method
Nitrogen
A
A
Compendium of Analytical Methods
46
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Nitrogen
aqueous solution of carbamide and ammonium nitrate
Dichloromethane
mixtures (nonaqueous liquids)
Dichloromethane
adhesives, paints,
Reference for internal methods
Analytical technique
Sample preparation
Note
BSS EN15750:2010 Method А; BSS 1378:1977 т.3.1
Distillation apparatus. Automatic titrator.
Reduction, hydrolysis, A distillation, titration
EPA METHOD 8260C
GC-MS
EPA Method 5035A (solvent extraction - water dilution) / EPA Method 5021 (Headspace analysis)
A
GC-MS
~ 0,05 g sample / 100 ml solv.
D/ 0.04%
GC-ECD
brominated derivative extraction into ethyl acetate
A
59. Dichloromethane CAS No 75-09-2 EC No: 200-838-9 59.1. Paint strippers
60. Acrylamide CAS No 79-06-1 Substance / mixtures Acrylamide
aqueous extract of solid samples
61. Dimethylfumarate (DMF) CAS No 624-49-7 ; EC 210-849-0 Articles / parts thereof
EPA 8032A
Compendium of Analytical Methods
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
47
Analyte
Matrix/Product
Analytical method
Reference for internal methods
Dimethylfumarate
leather, desiccant, textiles
Internal method
Dimethylfumarate
shoes/ leather/ plastics
Internal method
Dimethylfumarate
leather and textiles
Analytical technique
Sample preparation
Note
HPLC-DAD 1.Biomed, Chromatograpy, 2011;25, 1315-1318 2.ISO/TS 16186
1,000 g extraction in methanol in an ultrasonic bath for 60 min
B
ISO/TS 16186
GC-MS
1g sample + 10 ml acetone + Istd
A
HPLC-DAD
Extraction with methanol
D / 0.02 [mg/kg]
ASU §64 LFGB K 84.00-29 (2011) (ca. 100 mg Material + 3 ml HNO3 + 0,5 ml HCl bei 200°C in Mikrowelle)
A
63. Lead CAS No 7439-92-1 ; EC No 231-100-4 and its compounds 63.1. Individual parts of jewellery articles Lead
metals
Internal method
Aufschluss: ICP-OES - ASU §64 LFGB K 84.0029 (2011) Messung: - J. Nölte: ICPEmissionsspektrometrie für Praktiker, Wiley-VCH Verlag GmbH, Weinheim, 2002 - DIN EN ISO 11885: 2008 (D)
Compendium of Analytical Methods
48
Restriction
Restriction
(Annex XVII entry number and analyte/s covered)
(Annex XVII sub entry: paragraph number, analyte and matrix/product covered)
Analyte
Matrix/Product
Analytical method
Lead
metals
EPA 6020A
Lead
metals
Reference for internal methods
Analytical technique
Sample preparation
Note
ICP-MS
EPA 3051A: microwave digestion with HNO3 and HCl 3:1
A
XRF or XRD
D / Lead 0.01% Lead compo unds 5 %
Compendium of Analytical Methods
49
Appendix 1-Glossary 1.
LIST OF ACRONYMS
Term or abbreviation
Definition
AAS
Atomic absorption spectroscopy
ASTM standards
Standards developed by the American Society for Testing and Materials
DAD
Diode array detector
DIN standards
Standards developed by the “Deutsches Institut für Normung” (German Institute for Standardisation)
ECD
Electron capture detector
ECHA
European Chemicals Agency
EDXFR
Energy dispersive X-ray fluorescence
EI
Electron Ionisation
EN Standards
Standards developed by the European Committee for Standardisation
EU
European Union
FID
Flame ionisation detector
GC-ECD
Gas chromatography with electron capture detector
GC-FID
Gas chromatography with flame ionisation detector
GC-MS
Gas chromatography mass spectrometry
HG-AAS
Hydride generator atomic absorption spectroscopy
HPLC
High performance liquid chromatography
HPLC-DAD
High performance liquid chromatography diode array detector
HPLC-FLD
High-performance liquid chromatography with fluorescence detection
HSGC
Headspace gas chromatography
ICP-MS
Inductively coupled plasma mass spectroscopy
ICP-OES
Inductively coupled plasma optical emission spectroscopy
ISO standards
Standards developed by the International Organisation for Standardisation
Compendium of Analytical Methods
50
Term or abbreviation
Definition
LOD
Limit of detection
MS
Mass Spectrometry
MSZ standard
Standard developed by the Hungarian Standards Institution
MTBE
Methyl Tertiary Butyl Ether
NEA
National enforcement authority
NIOSH
National Institute for Occupational Safety and Health of the United States of America
NLV
REACH Annex XVII restrictions without a limit value
PBB
Polybrominated biphenyl
PCA
Polycyclic aromatics
PMU products
Permanent Makeup Products
PVC
Polyvinyl chloride
REACH
Regulation (EC) No 1907/2006 of the European Parliament and of the Council of 18 December 2006 concerning the Registration, Evaluation, Authorisation and Restriction of Chemicals
SEM-EDS
Scanning Electron Microscopy and Energy Dispersive Spectrometry
SPE
Solid Phase Extraction
US EPA
Environmental Protection Agency of the United States of America
UV
Ultraviolet
XRD
X-ray diffraction
XRF
X-ray fluorescence
Compendium of Analytical Methods
2.
KEY TERMS
Applicability: the set of information about the identity of analyte(s), the concentration range and the kind of matrix/material/item of a specific analytical method for its intended application. Limit of detection (LOD): the lowest concentration or mass of an analyte, which can be detected with acceptable certainty, even though it cannot be quantified with acceptable precision. Measurement uncertainty: the non-negative parameter characterising the dispersion of the quantity values being attributed to a measure and based on the information used Qualitative methods: analytical methods which allow to identify the presence of a substance on the basis of its chemical, biological or physical properties. These methods do not enable a conclusive judgement for enforcement purpose and entail a confirmatory analysis Performance characteristic: functional quality that can be attributed to an analytical method. This may be for instance accuracy, trueness, precision, repeatability, reproducibility, recovery, LOD and LOQ. Performance requirements: requirements for a performance characteristic according to which it can be judged that the analytical method is fit for the purpose and generates reliable results. Recovery: the fraction of the analyte that is recovered after addition of a known amount of the analyte, under defined conditions to the sample, when the test sample is analysed using the entire method. Reproducibility: precision under reproducibility conditions, namely the distribution of measurement results obtained under reproducibility conditions. Reproducibility conditions: conditions where test results are obtained with the same method on identical test items in different laboratories with different operators using different equipment. Screening methods: analytical methods that are used to detect the presence of a substance or class of substances at the level of interest. These methods have the capability for a high sample throughput and are used to sift large numbers of samples for potential non-compliant results.
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ECHA-15-R-18-EN - ISBN: 978-92-9247-648-9 - DOI: 10.2823/399943
european chemicals agency annankatu 18 , p.o. box 400, fi - 00121 helsinki, finland echa.europa.eu
